3,4-Dihydro-2H-pyrane-2,4-diones

ABSTRACT

A compound of the formula   WHEREIN X is hydrogen or halogen: R1 is alkyl having six or less carbon atoms or phenyl; R2 is alkyl having 1 to 20 carbon atoms or haloalkyl having six or less carbon atoms or phenyl or phenyl substituted with halogene or nitro or benzyl or phenoxymethyl or 2-phenylvinyl; R3 is hydrogen or alkyl having 1 to 10 carbon atoms or alkenyl having six or less carbon atoms or alkynyl having six or less carbon atoms or benzyl; and THE PROVISO THAT R1 and R2 don&#39;&#39;t represent simultaneously methyl group; IS USEFUL AS HERBICIDE.

United States Patent 1 Sawaki et al.

3,4-DIHYDRO-2H PYRANE-2,4-DIONES Filed: 0a..1'5, '1973 Appl. No: 406,621]

Assignee:

Foreign Application Priority Data Oct. 20, i972 Japan 47404962 Dec. 25. 1972 Japan 47-2526 Dec. 25. i972 Japan 47-2527 US. Cl ..-260/343.5; 260/240 R; 71/88;

424/279 int. Cl. C07D 309/30 Field of Search 260/3435, 240 R References Cited FOREIGN PATENTS OR-APPLlCATlONS 5/1971 Japan 260/3435 1 Dec. 16, 1975 Primary ExaminerPaul M. Coughlan, Jr. Assistant Examiner-Anne Marie T. Tighe Attorney, Agent, or Firm-George B. Oujevolk [57] ABSTRACT A compound of the formula 0 X an-@42 wherein X is hydrogen or halogen:

R is alkyl having six or less carbon atoms or phenyl;

R, is alkyl having 1 to 20 carbon atoms or haloalkyl having six or less carbon atoms or phenyl or phenyl substituted with halogene or nitro or benzyl or phenoxymethyl or 2-phenylvinyl;

R is hydrogen or alkyl having I to 10 carbon atoms or alkenyl having six or less carbon atoms or alkynyl having six or less carbon atoms or benzyl; and

the proviso that R, and R don't represent simultaneously methyl group;

is useful as herbicide.

9 Claims, 30 Drawing Figures US. Patent Dec. 16, 1975 Sheet 1 of 10 3,927,034

F I G. I

BUMPUUND No.2 ("/01 gm 2 a0 5: an E an 5 20 a: Inns 1900 1 1600 1 WAVE NUMBER (crfi) F I G. 2

GUMPUUND Nl].3

WAVE NUMBER (crfi') 3 numpuuuu mun WAVE NUMBER (crri) U.S. Patent Dec. 16,1975 Sheet2of10 3,927,034

F l 6.4 0/0) OOMPOUNO N019 100 2 an 2 an E 40 g 20 0 WAVE NUMBER (crfi) F I G. 5 OOMPOUNO NOR? glfl O 2 an an E 40 g 20 51' O WAVE NUMBER (on?) F I 6 OOMPOUNO NO.3O

PEROENT TRANSMISSION Q IOOO 1200 1] \OOO BOO WAVE NUMBER (cni) U.S. Patent Dec. 16, 1975 Sheet3of 10 3,927,034

7 COMPOUND No.49 (96) 3100 21m 2 an E40 E20 WAVE uumaen (cni) (0/0) 8 COMPOUND Nl].55 glut! gm 60 Em g2 WAVE NUMBER m) F I 9 cnmPouun No.58 gull] 2 so 2 an E 40 g 20 WAVE NUMBER (crri) U.S. Patent Dec. 16,1975 Sheet40f 10 3,927,034

F I G. IO 0/0) BUMPUUNU NUS? gIUU 2 so 2 an E 40 g 20 WAVE NUMBER (cni F I G. I I (0/0) BBMPUUNB NUBB 5100 2 so 2 so E 40 g 20 WAVE NUMBER c F I G12 uumpuuuo NlLfiB PERBENI TRANSIISSIBNA z a s 2 g WAVE NUMBER mm) U.S. Patent Dec. 16,1975 SheetSof 10 3,927,034

FIG. 3 (0/0) I COMPOUND NU.1

WAVE NUMBER (crri') F I 6. I4 [9. BUMPUUND NM 2- 100 gen 50 Em gm 0 WAVE NUMBER (cni) F I GUMPUUND M35 2100 2am gm E40 E20 6; 0

WAVE NUMBER (crri') US. Patent Dec. 16,1975 Sheet60f 10 3,927,034

F I (5. I6 (0/0) BUMPUUNU NUB? 100 gen 2 so 5 40 E 20 0 WAVE NUMBER (cni) F I G./7

BBMPBUNU RUM PERCENT TRANSMISSI N WAVE NUMBER (cni) 6. /0, ,8 BUMPUUND NM? PERCENT TRANSIISSIUIL WAVE NUMBER (crri') US. Patent Dec. 16, 1975 Sheet 7 of 10 3,927,034

FIG.I9

UUNPUUNU NU.43

ISSIUN PERCENT TRANS! WAVE NUMBER (0126') compnuun No.44

PERCENT TRANSNISSI N WAVE NUMBER (cni) F l 2 I GUMPUUND NU.45

PERCENT TRANSNISSI w a s 2 2 5 WAVE NUMBER (cni') U.S. Patent Dec.16, 1975 Sheet8of 10 3,927,034

F I 6.22 BUMPUUND NMB 100 280 2511 E40 520 K [1 WAVE NUMBER (crri') F I 6.23 0/0) COMPOUND No.50 zmu PERCENT THANSMSS WAVE NUMBER (cni) A,, H624 cumpnuun N0.51 gm] as 260 E40 E20 WAVE NUMBER (cn'i) U.S. Patent Dec. 16, 1975 Sheet 9 of 10 3,927,034

' F I 6.25 W0) BUMPUUND No.12

PERBENT TRANSIISSIUN WAVE NUMBER (crri) F I 6.26 c COMPOUND N013 1 011 i; an 2 60 E40 E20 2 0 WAVE NUMBER (crri') F I 6.27 (%1 GUMPUUND N015 WAVE NUMBER (crri) US Patent Dec. 16, 1975 Sheet 10 of 10 3,927,034

UUMPUUNU N015 PERCENT TRANSMISSION A z a s 2 2 5 WAVE NUMBER (crfi) FIG.29

(0/0, COMPOUND mm WM NUMBER (cni) F I comvounn N0.81

PERBENI TRANSIISSIUI A c r; s s s 25? WAVE NUMBER (on?) 3.4-DIHYDRO-2H-PYRANE-2.4-DIONES The present invention relates to novel compounds of 3.4-dihydro-2H-pyrane-2.4-diones. the process for the preparation thereof and their uses as herbicides having selective activity and plant growth regulator.

Further. this invention relates to herbicidal and plant growth regulating compositions containing one or more of novel compounds. and to the method of combatting weeds and regulating the plant growth which comprises applying to plant or to soil the said compounds.

ln addition to the above-mentioned effects the compounds of the present invention show both acaricidal and fungicidal activities.

lt is an object of the present invention to prepare new 3.4-dihydro-2H-pyrane-2.4-diones and metal salts thereof.

Another object is to prepare improved compositions and processes for killing undesired plants.

The inventors synthesized quite a few compound of 3.4-dihydro-2-H-pyrane-2.4-diones derivatives and tested the biological activities for the compounds.

As the result of the test. it has been discovered that the new and novel compounds of the present invention are particularly effective as herbicides and plant growth regulators.

The novel compounds of this invention are characterized by the following formula:

wherein X is hydrogen or halogen;

R, is alkyl having six or less carbon atoms or phenyl;

R is alkyl having l to carbon atoms or alkyl having l to 20 carbon atoms substituted with halogen or phenyl or phenyl substituted with halogen or nitro or benzyl or phenoxymethyl or 2-phenylvinyl;

R is hydrogen or alkyl having I to 10 carbon atoms or alkenyl having 6 or less carbon atoms or alkynyl having 6 or less carbon atoms or benzyl;

a proviso, R, and R does not represent simultaneously methyl group and metal salts of the above formula compounds.

However. it is expected that the compound of the present invention has the following three chemical formulae because of it's tautomerism The compounds are particularly effective as selective herbicides for grass weeds such as annual bluegrass (Poa annua). water foxtail (Alopecurus aequalis). large crab-grass (Digr'raria adscendens) and others in both soil treatment and foliar treatment. especially it has now been found that the compounds hardly injure leguminous plants such as adzuki bean (p/raseolus angularis) and soy bean (Glycinemax) and broad leaf plants such as suger beets which easily suffer phyto-toxicity.

It is already known that 4-hydroxy-6-methyl-a-piron derivatives has herbicidal properties as shown in Japanese Pat. Publication No. l69l6/197l.

But in order to wither completely to death the said grass weeds, a large amount of the above herbicidal chemical is required and this is one drawback for above mentioned herbicidal agent.

ln the other words. according to the descriptions of above mentioned public patent belletin and the results of the later additional experiments by the inventors. a chemical amount containing 500 g of effective component. in proportion to ID a. of area is able to give an expected effect in the case of employing it practically but another chemical amount containing 250 g of effective component. in proportion to If) a. of area is not able to wither all miscellaneous grasses to death. in the other words. it cannot give a perfect herbicidal effect. But. in the event of employing the compound of the present invention as a herbicidal agent. a chemical amount containing 250 g of effective component. as a matter of course, further a chemical amount containing I25 g or less of effective component. in proportion to l0 a. of area. in compliance with the same treating method of conventional herbicidal agents indicates a strong herbicidal effect and thereby a perfect herbal prevention and extermination can be expected.

As a surprising matter. some kind of the compound by the present invention in the event of applying it to barnyard grass with a soil treatment by water stagnation indicates 30 multiples or more of herbicidal effect. in comparison with the effect of above mentioned conventional compounds.

In case of foliar treatment using the compounds of the present invention. even the same amount of chemical which makes barnyard grass of grass weed completely kill gives no damages to broadleaf plants such as radish. soy bean (Glycine max). garden pea (Pisum sarrvum), spinach (Spinacia vleracea) and sugar beets at all. and in case of soil treatment before germination. even the same amount of chemicals which prevents large crab-grass (Digiraria adscendens) germinating gives no damages to seeds of broad leaf plants at all.

As mentioned above. a secure safety to the broadleaf crop against phytotoxicity of the herbicidal agent is extremely high and as to its application. in the other words. its applicable period. its applying location and its applying concentration. it has a very broad extent and it can be used in the wider extent.

It has been further found that the new compounds of the present invention have both dwarfrng effect which control the excess growth of perennial plant. particularly lawn and inhibition effect of heading.

X P n al-04x Though lawn which is one of industrial crops is widely grown in gardens and golf rinks. it is very troublesome to trim it well. particularly in summer lawn grows well. a large labor power is employed for mowing it and further heading spoils remarkably its beautiful sight.

The compounds of the said general formula can be applied to the soil or leaves. and show the dwarfmg effects. inhibitions of heading and runner for lawn without injury.

The compounds of the present invention shows plant growth regulating effect of controlling the growth of new buds without giving any damages to developing leaves and stems of broad leaf crops when the compounds are used in greater quantities than the compounds are used to have the effects of killing weeds and the activity of selective herbicides for broad leaf crops.

Growth inhibiting effect for new buds of broad leaf crops prevents sucker growth of tobacco or chrysanthemum, stops useless nutritive growth of fruit-trees or beans and further change the said growth to reproductive growth. These controlling effects are very useful for cultivating crops.

It is another advantage of the present invention that a residual toxicity in the soil or the plant and an acute toxicity for warm blooded animals and fishes are not feared because the said compounds can be employed with a low chemical concentration. The invention will be more readily understood from the following detailed description and the accompanying drawings in which FIGS. 1 through 30 show infrared spectrum for the compounds described herein.

The compounds of this invention can be prepared in accordance with the following equation;

nol, ethanol or dimethylformamide and both components are made to react each other, if necessary, by means of heating step and thereby the sodium salt or the potassium salt can be obtained. Further, if the said sodium salt or the said potassium salt is made to react similarly with other kinds of above mentioned metal salt, the objective metal salt can be obtained. In numerous cases, the said metal salt is scdimented as a precipitate or as a crystal in above mentioned solvent.

Some metal salt of the present invention produced with above mentioned process may cause partially a chemical change or a decomposition at a high temperature, so that it does not show a clear melting point. Therefore, by applying Infrared ray absorptive spectrum to the raw material and the reaction compound, a formation of the metal salt can be identified through a transference of absorption band and a change of absorption intensity. In the other words. the raw material compound having the said general formula [[1 indicates 7 an absorption of carbonyl group at a wavelength range 0 on u 9 Na-o-R w 3 NH2O-R3 R1 4 o 0 R1 o I] [I I] wherein R,, R. R and X represent the aforesaid meanmgs.

In practical method the compounds of this invention are prepared through the reaction of general formula [I] with the general formula ill] in inert solvent.

As a inert solvent, acetone, ether, methylalcohol. ethylalcohol. isopropylalcohol, behzene, dimethylforrnamide chloroform, acetonitrile, dichloroethane. dichloromethane, ethyl acetate. dioxane, toluene. xylene and dimethyl sulfoxide etc. are used, but preferably methylalcohol, ethylalcohol, isopropylalcohol, acetonitrile, dimethylfonnamide, dioxane, ether and chloroform are used.

Reaction temperature is from l0C to the boiling point of employed solvent, preferably from l0 to and the reaction terminates between 0.5 and several hours.

Furthermore a little amount of toluenesulfonic acid, hydrogen chloride gas and Lewice acids such as trifluoroboron and alminum chloride can be added as a catalyst. if necessary.

After the reaction terminated, lthe solvent. if necessary. is replaced and then, the reaction mixture is extracted with an'alkaline solution and further, an alkaline layer is acidified withhydrochloric acid, whereby the crude product is isolated from the reaction mixture by extraction with solvent or by filtration.

In case of crystalline substance. the crude product can be purified by recrystallization and in oily substance the crude product can be purified by distillation or isolation by column chromatography.

A chemical structure for the resulting purified compound can be confirmatively identified by means of an elementary analysis, NMR spectrum and IR spectrum.

In the case of producing the metal salt of the compound by the present invention, above mentioned compound having the said formula [Ill] is homogeneously mixed with caustic soda or caustic potassium in the presence of an organic solvent such as acetone, methaof i720 to i730 cm, whereas the corresponded metal salt shows the absorption at a side of longer wavelength. Further, in some occasion, an anion such as OH may be simultaneous coordinated with a metal atom of some metal salt obtained above.

ln order to facilitate a clear understanding of the invention, the following preferred specific embodiments are described as illustrative and not as limiting the invention.

EXAMPLE l Process for producing 3-[ l(N-allyloxyamino)propylidene]-6-methyl-3,4- dihydro-2H-pyran-2,4-dione l.8 g (0.0] mol) of 4-hydroxy-6-methyl-3-propionyla-pyrane was dissolved in l0 c.c. of ethanol and 0.8 g (0.0l l mol) of allyloxy amine was added in the resulting solution and then, it was agitated durng 2 hours at room temperature. Further, it was agitated during 30 minutes at a temperature of about -80C and then ethanol was distilled off from it under a reduced pressure and a residue was dissolved in chloroform. The resulting chloroform solution was extracted for two times with a caustic soda solution having 5 of concentration by an amount of 7-8 c.c. and an alkaline layer produced thereto was hydrochlorinated and thereby, an oleo-material was visibly sedimented. The said oleo-material was extracted for two times with ID c.c. of chloroform and the resulting chloroform layer produced thereto was rinsed with water and it was dried with magnesium sulfate. The resulting chloroform was distilled off under a reduced pressure and thereby 2 g of 3-[l(N-allyloxyamino)propylidene1-6 'methyl 3,4-dihydro-2H-pyran-2,4-dione, indicating colorless oily was obtained with 84 of yield rate. Refractive index n l.53ll. Elementary analysis Found: C, 60.70; H. 6.35; N, 5.96. Calculated for C, H NO,: C, 60.75; H. 6.37; N. 5.90.

EXAMPLE 2 3.0 g (0.015 mole) of 3-butyryl-4-hydroxy-6-methyla-pyrone was dissolved in 20 c.c; of ethanol and further. 1.2 g (0.017 mol) of allyloxyamine was added in it and the resulting solution was continuously agitated firstly at a room temperature during 2 hours and secondly at a temperature of about 70-80C during 30 minutes. I

Afler having carried out acooling step for it, ethanol was distilled off from it under a reduced pressure and a residue was dissolved in 'chlorofonn and the resulting chloroform solution extracted for two times with c.c of caustic soda having 5 of concentration. A resulting alkaline layer produced thereto was hydrochlorinated and a resulting sedimented material was extracted with 15 c.c of chloroform and a resulting chloroform layer was rinsed with water and then, it was dried with magnesium sulfate. Then, the chloroform layer was distilled off and ,aresidual material was recrystallized with n-hexane and thereby 2.8 g of 3-[1- (N-allyloxyamino)butylidene] 6-methyl3,4-dihydro- 2H-pyran-2.4-dione, as acolorless crystal was obtained with 74 of yield rate.

Melting point: 52-54C.

Elementary analysis Found: C, 62.10; N, 5.61. Calculated for C H NO C. 62.14 N, 5.57. J

EXAMPLE 3 Process for producing 3-[ l-(N-ethoxyamino)propylidene)]-6-ethyl-3.4-dihydro-2H-py' ran-2,4-dione 2.0 g (0.01 mol) of 6=ethy1-4-hydroxy-3propionitrile-a-pyrone and 0.66 (0.01 1 mol) of ethoxyamine were employed and the "same reaction operation in Example 2 was carried out and thereby, 2.0 g of 3-1 1- (N-ethoxyamino)propylidenel-6-ethyl-3,4-dehydro- ZH-pyran-dione, as a colorless crystal, was obtained with 83.0 of yield rate.

Melting point: 54-55C.

Elementary analysis Found: C, 60.19; H. 7.10; N. 5.90. Calculated for CggH NOn-C. 60.25; H, 7.1 l; N, 5.86

EXAMPLE4 Process for producing 3-[ 1-( N-ethoxyamino)butylidene1-6-propyl-3,4-dihydro 2H-pyran' 2A-dione EXAMPLE 5 Process for producing 5-bromo-3-[ l-(N-ethoxyamino)propylidene1-6-ethyl- 3,4-dihydro-2H-pyran-2.4-dione 1.4 g of 5-bromo-6-ethyl-4-hydroxy-3-propionyl-apyrone (a melting point of 765C to 77.5C) was dissolved in 10 c.c of ethanol and further 0.5 g of ethoxyamine was added in it and the resulting solution was agitated at room temperature during 4 hours. Further, it was agitated at a temperature of 4050C during 30 minutes. Then, above ethanol was distilled off from the resulting reaction mixture under a reduced pressure and thereby, a crude white crystal was obtained. Further, the crude white crystal was recrystallized by using n-hexane and thus, a white spicular crystal was obtained as an objective compound.

Melting point: 46-47C Yield amount: 1.3 g (Yield rate: 81

EXAMPLE 6 Process for producing 5-bromo-3-[ l-(N-allyloxyamino)butylidenel-6-propyl- 3,4-dihydro-2H-pyran-2,4-dione 1.5 g of 5-bromo-3-butyl-4-hydroxy-6-propyl-apyrone (a melting point of 50-5lC) was dissolved in 10 c.c of ethanol and 0.6 g allyloxyamine was added in it and the resulting solution was agitated at room temperature during 4 hours and further, it was continuously agitated at a temperature of 4050C during 30 minutes. Then, above ethanol was distilled off from above resulting solution under a reduced pressure and thereby, a colorless. viscous liquid was obtained. The said colorless, viscour liquid was dissolved in 10 c.c. of ether and this solution was extracted for 2 time with 20 c.c of aqueous solution containing 5 concentration of caustic soda. Then, the resulting caustic soda solution was acidified with concentrated hydrochloric acid under cooling conditions and thereby an oleo material was sedimented in it.

The said oleo-material was separated from the solution and it was extracted for 2 times with 10 c.c ofether and an ether layer obtained thereto was rinsed with water. The said ether layer was dried with magnesium sulfate and then, the ether layer was distilled off under a reduced pressure and thus, a light yellowish oleomaterial was obtained as an objective material.

Refractive index: n,,' 1.5535

Yield amount: 1.6 g (Yield rate: 93%) EXAMPLE 7 Sodium salt of 3-( l-N-allyloxyaminobutylidene )-6-methyl-3 .4-dihydro-2H-pyran-2.4-dione 2.5 g of 3-( l-N-allyloxyaminobutylidene)6-methyl- 3.4-dihydro-2H-pyran-2.4-dione were dissolved in 20 cc of acetone. and to which 0.4 g of sodium hydroxide dissolved in 2 cc of water was added gradually under agitation at room temperature. White crystal of sodium salt were obtained. Yield 2.7 g

m.p. l l4-l 16C infrared spectrum: 1660 cm (C=O) EXAMPLE 8 Nickel salt or 3-( l-N-ethoxyaminopropylidene)-6-methyl-3.4-dihydro-2H-pyran-3,4 -dione 2.3 g of 3-( l-N-ethoxyaminopropylidene)-6-methyl- 3,4-dihydr-2H-pyran-3.4-dione were dissolved in 20 cc of acetone and to which 0.4 g of sodium hydroxide dissolved in 2 cc of water was added under agitation. Agitation was continued for l0 min.. to the reaction mixture 1.2 g of nickel chloride (NiCloH O) dissolved in 2 cc of water was added under agitation. Green crystal of nickel salt were obtained. Yield 2.4 g (95 70) m.p. 2l8-2l9C (with decomposition) infrared spectrum (C=O) 1683 cm" EXAMPLE 9 Copper salt of 3-( l-N-ethoxyaminopropylidene) 6-ethyl-3 .4-dihydro- 2H-pyran-2,4-di one By a procedure in similar to Example 8. from the reaction of 2.4 g of Copper salt of 3-(l-N-ethoxyaminopropylidene)-6-ethyl-3.4-dihydro-2H-pyran- 8 2.4-dione, 0.4 g of sodium hydroxide and 1.25 g of copper sulfate (CuSO -H O), dark agreen crystals of copper salt were obtained. Yield 2.7 g 100 m.p. l72-l74C (with decomposition) infrared spectrum: 1673 cm (C=O) EXAMPLE i0 Barium salt of 3-( l-N-ethoxyaminopropylidene)-6-ethyl-3.4-dihydro- 2H-pyran-2.4-dione By a similar procedure to Example 8. from the reaction of 2.4 g of 3-( l-N-ethoxyaminopropylidene)-6- ethyl-3,4-dihydro-2H-pyran-ZA-dione, 0.4 g of sodium hydroxide and L2 g of barium chloride (BaCl -2H O), crude crystals were obtained.

The crude crystals were dissolved in 99.5 ethanol and unsoluble substances were taken away from it, 2.8 g of white dust crystal was obtained with 90 of yield rate.

m.p. over 300C infrared spectrum I673 cm (c=o) In addition to the above mentioned compound described in the preceding examples, some typical compounds of the present invention are listed in Table I.

Table l Com Chemical Name Physical Constant pound No.

l 3-( l-N-ethoxynminopropylidene)-6-methyl-3.4-dihydro-2H-pyran-2.4-dione m.p. 57 58C 2 3-( l-N-allyloxyaminopropylidene)-6-methyl-3.4-dihydro-2H-pyran-2.4-dione refractive index a m, 1.5720 3 3-( l-N-ethoxyaminobutylidene)-6-methyl-3.4-dihydro-ZH-pyran-2.4-dione m.p. 38 40C 4 3-( l-N-allyloxyaminobutylidene)-6-mcthyl-3.4-dihydro-2H-pyran-2.4-dione m.p. 52 54C 5 3-( l-N-ethoxyaminopentylidene)-6-methyl-3.4-dihydro-2H-pyran-2.4-dionc m.p. 36 38C 6 3-( l-N-allyloxyaminope'ntylidene)-6-methyl-3.4-dihydro-2H-pyran-2.4-dione refractive index Y m 1.529) 7 3-(] Nethoxyamino-2.2-dimethylpropylidene)-6-methyl-3.4-dihydro-2H-pyran-2.4-dione mip. I77 178C 8 3-( l-N-allyloxyamino-2 2-dimethylpropylidene)6-methyldA-dihydro-ZH-pyran-2.4-dione m.p. I27 l29C 9 3-( l-N-ethoxyaminohexylidene)-6-methyl-3.4-dihydro'2H-pyran-2.4-dione m.p. 55 56C It) 3-( l-N-allyloxyaminohexylidene)-h-methyl-3.4-dihydro-2H-pyran-2.4-dione rcfractive index n,," l.$236 l l 3-( l-N-ethoxyarninodecylidene)-6rnethyl-3.4-dihydro-2 H-pyran-2.4-dione refractive index mi" [.5053 I2 3-( l-N-aliyloxyamlnodecylidene)-6-methyl-3.4-dihydro-2H-pyran-2Adione refractive index n," I.5l35 l3 3-( l-N-allyloxyaminododecylidene) fi-methyl-l.4-dihydm-ZH-pyran-ZA-dione m .p. 36 38C l4 3-( l-N-allyloxynminohexadecylidene)-6-mcthyl-3.4-dihydro-2H-pyran-2.4-dione m.p. 48 49C 3-( l-N-allyloxyaminooctadecylidcne)-6-methyl-3.4-dihydro-2H-pyran-2.4-dionc m.p. S4 56C to 3-( I-N-ethoxyarnino-4-chlorobutylidcne)-6-methyl-3.4-dihydro-2H-pyrun-2.4-dione refractive index n,, 1.5341 l7 3-( l-N-allyloxyamino-4 chlorobutylldene)-6-mcthyl-3.4-dihydro-2H-pyran-2.4-dionc refractive index m, l.5377 l8 3-tl-N-ethoxyuminobenzylidene)-6-methyl-3.LdihydroQH-pyrun-Z.4-dione m.p. I84 I85C V (with decomposition) l9 3-( l-N-ullyioxyamlnobenzylidenei-o-methyl-3.4-dihydro-2H-pyran-2.4-dlone m.p. I42 I44C 2t) 3-( l-N-allylox 'nmino-p-chlorobenzylidene)-6-methyl-3.4-dihydro-2H-pyran-2.4-dlone m.p. I39 l4lC 2| 3-( l-N-allyloxyamino-p-nltrobenzylidene)-b-methyl-3.4-dihydro-2H-pyran-2.4-dione m.p. I42 143C 22 3-( l-N-ethoxyamino-Z-phenylethylidene)-6-methyl-3.4-dihydro-2H-pyran-2.4-dione refractive index us 575 23 3-( l-N-ethoxyamino-2-phenoxycthylidene) 6-methyl'3.4-dihydro-2H-pyran-2.4-dione m.p. 93 94C 24 3-( l-N-ethoxyaminocinnamylidene)-6-methyl-3.4-dihydro-2H-pyran-2.4-dione m.p. 65 66C (with decomposition) 25 3-( l-N-allyloxyuminocinnarnylideneI-6-methyl-3.4dihydro-2H-pyran-2.4-dione refractive index n L583) 26 3-( l-N-allyloxyaminoethylidcne)-6-ethyl-3.4-dihydro-2H-pyran-2.4-dione m.p. 39.5 C 27 3-( I-N-h -droxyaminopropylidcne)-6-ethyl-3.4-dihydro-2H-pyrun-2.4-dione m.p. l6l-l62C K (with decom$sitionl 28 3-! l-N-methoxyamlnopropylidene)-6-ethyl-3.4-dihydro-2H-pyran-2.4-dione m.p. 43 44 t 29 3-( l-N-ethoxyaminopropylidene)-6-ethyl-3.4-dihydro-2H-pyran-2.4-dione 54 C 30 3-( l N-propoxyaminopropylidene)-6-ethyl-3.4-dihydro-2H-pyran-2.4-dione reggactive index n" l.53l5 3t 34 l-N-isopropoxyamlnopropylidene)-6 ethyl-3.4-dihydro-2H-pyran-2.4-dione m.p. 44 46C 32 3-( l-N-allyloxyamlnopropylldene i-fi-ethyl-SA-dihydro-2H-pyran-2.4-dionc regr a tivesindex LI: a n 1.5 89 33 3-( l-N-propargyloxy-aminopropylidene)-6-ethyl-3.4-dihydro-2H-pyran-2.4-dionc m.p. 84 86C 34 3-( l-N-n-butoxynminopropylldene)-6-ethyl-3.4-dihydro-2H-pyrnn-2.4-dlone refractive index 1 n "l.5l69 3S 3-( l-N-hexyloxyaminopropylidenel--ethyl-J.4-dihydro-2H-pyran-2.4-dione reEra ctive index 1 n,,' l.5l7O 36 3-( l-N-benzyloxyaminopropylidene)-6-ethyl-3.4-dlhydro-2H-pyran-2.4-dione m.p. 63 C 37 3-( l-Nethoxyaminobutylidene)-6-ethyl-3.4-dihydro-2H-pyrun-2.4-dione refractive index Compound No.

Hereinafter, the compounds of this invention are represented by Compond No/in Table 1.

The compounds of this invention can be applied 1 Table l-t :ttinued Chemical Name 3-( l-N-allyloxyarninobutylidene )-6-elh \i-L-S-dihydm-ZH-p)'run-2.4-dionc 3-(1-N-ethoxyaminobenzylidene)-6-ethy1-SA-tIihydro-IH-p run-IA-dione 3-(1-N-a1ly1oxyaminobenzylidene)-6-ethy1-3.4'dih dro-ZH -p\ mn-2.-) dione 3-t l-N-ethoxyaminoethylidene )-6'-n-propyl-3.4-dihydro-2H -p ran-2.4-dione 3 t l-N-ethoxyaminopropylidene )-6-n-propyl-3.4dih \dru-ZH-pyran-Z.4-dione 1-N-allyloxyaminopropylidene)-6-npropy1-3.4-dih dro- 2H-pyran-2.4-dione Physical Constant refractive index mp. 133 1 5C (with decomposition) mp 118 C m.p. s7 58C refractive index n 1.5265 refractive index 3-( 1-N-ethoxyamlnobutylidene)-6-n-propyl-3.4-dihydro-2H-pyrnn-2.4-dione regna ctlige index 3-( l-N-allyloxyaminobutylidene)-6-n-propyl-3.4-dihydro-2H-pyran-2.4-dione refractive index 3( l-N-ethoxyaminobe nzylidene )-6-n-propyl-3.4-dihydro-2 H-pyran-2.4-di0nc 3-( l-N-al1yloxyaminobenzylidene)-6-n-propyl-3.4-dihydro-2H-pyran-2.4-dione 3-t1-N-allyloxyaminopropylidene)-6-i-propyl-3.4-dihydro-2H-pyran-2.4-dione 3-( 1 -N-ethoxyaminopentylidene)-6-n-buty13,4dihydro-2H-pyran-2.4-dionc 3-( 1-N-ethoxyaminopropylidene)-6-i-butyl-3.4-dihydro-2H-pyran-2.4-dione 3-( l-N-allyloxyaminopropylidene)-6-i-butyl-3.4-dihydro-2Hpyran-ZA-dione mp. 153 154C m.p. I25 I26C refractive index n,," 1.5360 refractive index n,, 1.5148 refractive index n,," 1.5259 refractive index 3-( 1-N-ethoxyamino-3-methylbutylidene )-6-i-butyl-3.4-dihydro-2H-pyran-2.4-dione refractive index 3 (l-N-ethoxyaminoethy1idene)-6-phenyI-3.4-dihydro-2H-pyran-2A'dione m.p. 1 1 l l 13C 34 1-N-ethoxyaminopropylidene)-6-phenyl-3.4-dihydro 2H-pyran-2.4-dione mp. 80 81C 3( l-N-a1lyloxyaminopropylidene)-6-phenyl-3.4-dihydro-2H-pyran-2.4-dione m p 101 10 C 3-( 1-N-ethoxyaminobutylidene)-6-pheny1-3.4-dihydro-2H-pyran-2.4-dione m p 77 79C 3-( l-N-allyloxyaminobutylidene)-6-phenyl-3.4-dihydro-2H-pyran2.4-dione m p 64 66C 3-( l-N-ethoxyaminobenzylidene)-6-phenyl-3.4-dihydro-2H-pyran-2.4-dione m p 172 174C (with decomposition) 3-( l-N'allyloxyaminobenzylidene)-6-phenyl-3.4-dihydro-2H-pyran-2.4-dione m.p. I75 176C (with decomposition) 3-(1-N-ally1oxyaminopropylidene)6-bromo-6-methyl-3.4-dihydro-2H-pyran-2.4-dione m.p. 47 47.5C 3-( l-N-ethoxyaminobutylidene )-5-bromo-6-methyl-3.4-dihydro-2H-pyran-2.4-dione refractive index 3-( l-N-allyloxyaminobutylidene)-5-bromo-6-methyl-3.4-dihydro-2H-pyran-2.4-dione refractive index 3-( l-N-ethoxyaminopropylidene)-5-bromo'6 ethyl-3.4-dihydro-2H-pyran-2.4-dione m.p. 4b 47C 3-( l-N-allyloxyaminopropylidene)-5-bromo-6-ethyl 3.4-dihydro-2H-pyran-2.4-dione refractive index 3-( l-N ethoxyaminobutylidene)-5-bromo-6n-propyl-3.4-dihydro-2H-pyran-2.4-dione rei'ractive index 3( l-N-a1ly1oxyaminobutylidene)5-bromo-6-n-propy1-3.4-dihydro-2H-pyran-2.4-dione refractive index Nickel salt of 3-( l-N-ethoxyaminopropylidene)-6-methyl-3.4-dihydro-2Hpyran-2.4-dione Sodium salt of 3-(1 Ndullyloxyaminobutylidene)-6-methy1-3.4dihydro-2H-pyran-2.4-dione Nickel salt of 3-( l'-N-a11y1oxyaminobutylidene)-6 methy1-3.4-dihydro-2H-pyran-2.4-dione Copper salt of 3-(1-N allyloxyarninobutylidene)-6-rnethyI-3.4-dihydro-2H-pyran-2.4- dione mp. 218 219C (with decomposition) m.p. 114 116C m.p. 217 218C (with decomposition) m.p. 138 139C Zinc monohydroxide salt of 3-( 1-N-allyloxyaminobutylidene)-6-methyl-3.4-dihydro-2H- m.p. 300C up pyran-2.4-dione Calcium salt of 3-( l-N-ethoxynmlnopropy1ldene)-6-ethy1-3.4-dihydro-2H-pyran-2.4-dione m.p. 300C up Barium salt of 3-( l-N-ethoxyaminopropylidene)-6-ethyl-3.4dihydro-2H-pyran-2.4-dione m.p. 300C up Mangane salt of 3-( l-N-ethoxyaminopropylldene)-6-ethyl-3.4-dihydro-2H-pyranm.p. 300C up 2.4-d ione lron salt of 3-( 1-N-'ethoxyaminopropylideneH's-ethyl-3.4-dihydro-2H-pyran-2.4-dione Cobalt salt of 3-( l-N ethoxynminopropylidene)-6-ethy1-3.4-dihydro-2H-pyran-2.4-dione Nickel salt of 3-( 1-N-ethoxyaminopropy1idene)-6-ethyl-3.4 dihydro-2H-pyran-2.4-dione Copper salt of 3- (1-N-ethoxyaminopropylidenei-b-ethyl-S.4-dihydro-2H-pyran-2.4- dione Silver salt of 3-( 1N-ethoxyamlnopropylidene)-6-ethyl-3.4-dihydro-2H-pyran 2.4-dione sopropoxyaminopropylidene )-6-eth \-l-3.4-dihydro-2H -pyran-2.4-

m.p. 144 145C (with decomposition) m.p. 218 219C (with decomposition) m.p. 223 224C (with decomposition) m.p. I72 174C (with decomposition) m.p. 132 135C (with decomposition) m.p. 128C (with decomposition) m.p. 300C up m.p. 151- 152C area. preferably 100-500 g per 10a. of area. more preferably 200-300 g per 10a. of area.

The method of the present invention comprehends the employment of a liquid or solid composition condirectly to the soil as tare-emergence treatment or as 65 taining one or more of the present compounds as an post-emergence treatment and to plant foliage or they can be mixed intimately with the soil and may be applied to soil or foliar at rates of 50-4000 g per 10a. of

active component.

The active ingredient of this invention may be formulated by mixing with suitable carriers in a form generally used in agricultural chemicals such as wettable powder, emulsifiable concentrate. dust formulation. granular formulation. water soluble powder and aerosol.- As solid carriers. bentonite, diatomaceous earth. apatite. gypsum, talc. pyrophyllite. vermiculite. clay and others are used. As liquid carriers, kerosene. mineral oil. petroleum. solvent naphtha, benzene. xylene. cyclohexane. cyclohexanone. dimethylformamide. alcohol. acetone. and others areused. Sometimes surface active agent is added in order to give a homogeneous and stable fonnulation.

The compounds of this invention also can be applied admixed with other chemicals which are used in agronomic and horticultural management and are compatible with the compounds of this invention. Such chemicals can be. but are not restricted to. the classes of chemicals commonly known as plant nutrients. fertilizers. insecticides. acaricides. fungicides. herbicides and nematocides.

The concentrations of the active ingredients in the herbicidal and plant growth regulating compositions of this invention very according to type of formulation. and they are. for example. used in a range of 5-80 weight percent. preferably 20-80 weight percent. in wettable powders, 5-70 weight percent, preferably -50 weight percent. in emulsifiable concentrates. and 0.5- weight.percent. preferably l-lO weight percent in dust formulation.

Thus. a wettable powder or an emulsifiable concentrate produced thereto is diluted with water to a specified concentration and thereby, it is used as a liquid suspension or a liquid emulsion for treating the soils or the foliars leaf. Further. adust formulation is directly used for the soil treatment or the foliar treatment.

The non-limiting examples for the herbicidal and plant growth regulating compositions are illustrated as follows:

EXAMPLE 1 1 wettable Powder Parts by weight Compound I 50 Dintomaceous earth 2i Sodium ulkylauli'nte 9 Talc 20 These are mixed homogeneously and reduced to fine particles. Consequently, wettable powder containing 50 of active ingredient isobtained. in practical use. it is diluted to a certain concentration with water and is sprayed as a suspension.

EXAMPLE i2 wettable Powder Parts bv weight Compound 2 30 Diatomaceous earth 35 Sodium alkylsulfate 9 Talc 26 Consequently. emulsifiable concentrate containing of the active ingredient is obtained. in practical use. it is diluted to certain concentration with water and then is sprayed as an emulsion.

Example 14 Emulsifiable Concentrate Compound 4 50 xylene 30 dimethylformamide l2 polyoxyethylene phenylcther 8 These are mixed and dissolved.

Consequently. emulsifiable concentrate containing 50 of the active ingredient is obtained. in practical use. it is diluted to certain concentration with water and then is sprayed as an emulsion.

EXAMPLE l5 Dust Formulation Parts by weight Compound 5 l0 Talc 38 Bentonite 10 Clay 37 Sodium alkylsulfate 5 These are mixed homogeneously and micronized to fine particles. Fine particles is made into granules having the diameter in the range of 0.5-l .0 mm by granulatOl.

Consequently. dust formulation containing l0 of the active ingredient is obtained. In practical use it is directly applied.

EXAMPLE l6 Dust Formulation Parts by weight Compound 6 3 Talc 85 Bentonite 9 Carboxymethylcellulose 1 Sodium alkylsuli'ate 2 These are mixed homogeneously and micronized to fine particles. Fine particles is made into granules having the diameter in the range of O.5-l.0 mm by granulator.

Consequently, dust fonnulation containing 3 of the active ingredient is obtained. in practical use it is directly applied.

The compounds listed in Table I possess superior herbicidal and plant growth regulating activities compared to known compounds. further acaricidal and fungicidal activities.

Furthermore, it must be stressed that the compounds of this invention having most superior herbicidal activity are one according to the above-mentioned general formula [3] in which X is hydrogen, R. and R are alkyl having I to 4 carbon atoms, R;, is alkyl having 1 to 4 carbon atoms or allyl group or propargyl group.

The superior herbicidal, plant growth regulating, acaricidal and fungicidal effects of the novel compounds of this invention are clearly illustrated by the following tests.

As a compound for the comparison, B-(N-ethoxyacetoimidoyl)-4-hydroxy-6-methyl-a-pyrone for Test l 8 and calcium salt thereof for Test l-l3 which is described in the Specification of Japanese Pat. Publication No. l69l6/l97l were employed.

TEST 1 Preventive test for inhibitting sed germinations of weeds A soils containing a seed mixture of large crab-grass smooth pigweed and common purslane was packed in a vat having 780 cm of cross-sectional area. In the event of initiating seed germination of those weeds, test compound was prepared in similar manner to Example l l and was diluted with water to a specified concentration and a surface of above soils was treated by spraying the diluted aqueous suspension upon it. in the course of the 25th day after the spraying treatment, a growth state of weeds was investigated. A judgement standard for the growth state was classified as six grades in a range of 0-5 which has the following meanings:

no effect a few slightly burnt spots marked damage toleaves some leaves and parts of stalks partially dead plant partially destroyed plant completelydestroyedor --no germination The results were shown Table 2.

Table 2 Amount of. Growth state of the effective miscellaneous grasses component large crabsmooth common (g/ lOa.) grass pigweed purslane Test Compound No.

Table 2-c0ntinued Amount of Growth state of the Test effective miscellaneous grasses Compound No. component large crabsmooth common (g/ I On.) grass pigweed purslane 4| I25 5 0 0 62.5 5 0 0 250 5 0 l 42 I25 5 0 0 62.5 4 t) 0 250 5 l l 43 I25 5 l 0 62.5 5 0 0 250 5 2 2 44 I25 5 l I 62.5 5 0 O 250 5 l l 45 I25 5 0 I 62.5 5 0 0 250 5 l l 46 I25 5 0 I 62.5 5 0 0 The compound 250 5 0 l for the I25 3 0 l comparison 62.5 I 0 U Untreated 0 0 0 Soils TEST 2 Foliar treatment test The soils was packed in a vat having 780 cm of cross-sectional area and then, the seeds of large crabgrass and smooth pigweed were sowed and a covering soils was laid softly upon them and those seeds were made to grow in a greenhouse. In the occasion that those plants were grown to a stage of the second leaf period to the fourth leaf period, the test compound was prepared by the similar method of Example 1 l and was diluted to a specified concentration with water and the resulting diluted aqueous suspension by l/lOa. of amount was sprayed over the stem and the leaf of those plants and thereby, the spraying treatment was carried out. In the course of three weeks after spraying. the growth state of the plants was investigated. in compliance with the judging standard for the growth state defined in Test 1. results were set forth in Table 3.

Table 3 Growth state of Amount of miscellaneous grasses effective component (it/10a.)

Test Compound No. smooth pigwecd large crab-grass Table 3-continued Growth state of Amount of Compound effective component (3/ a.)

large crab-grass smooth plgweed The compound for the comparison Untreated O -l-Jwubbubuwaubbubauuaaupuupu O COCOO-'OO OCCC OOOO-OO-OO- TEST 3 Soil treating test Soil was packed in a pot and about grains of Barnyard grass seeds were sowed in it and a covering soils was softly laid upon them and the seeds were;

16 grass was investigated. In compliance with the judgement standard for the growth state stipulated in Test 1. this investigating results were set forth in Table 4.

Table 4 Amount of effective component (fl/liln.)

62.5 J l .3 l5 to Test compound No.

J-Ahabt-uuuuu cuiauu-aequco out-un- -utuuuuuiuiuimuuuvuvaviuivuuuoa The compound for the comparison Untreated Q utnuuuubuumuuuuu-uuu O cz uuiuimuux-z-utul-z-utc-uw TEST 4 Test for selective effect Soils was packed in a vat having 780 cm of cross sectional area and seeds of barnyard grass, red bean, radish, cucumber, beet and tomato were sowed in the said soils of the pot and a covering soil was softly laid upon them and then, those seeds were germinated and grown in a greenhouse. in the occasion that those crops were grown to a height of 5-8 cm, the test compound of emulsit'table concentrate prepared with prescription of Example 13 was diluted to a specified concentration and the resulting diluted emulsified agent by 100 l/lOa of amount was sprayed over the stems and leaves of those crops. In the course of two weeks after above treating step. the growth state of those crops was investigated with naked eye judgment. in compliance with the judging standard for the growth state defined in Test I, this investigating results were set forth in Table 5.

Table 5 Amount of grass Broadleaf plant Test effective weeds compound component barnyard Beet Cucu' Radish Red Tommutu No. tglloa.) grass ber bean l 150 5 0 0 0 0 0 2 150 5 u 0 0 0 o 3 150 5 0 0 0 0 0 4 I50 5 I 0 O 0 0 5 150 5 t) 0 0 n 0 I 6 150 4 t) t) 0 t) o 26 I50 4 0 (l O O 0 29 I50 5 l 0 0 0 o 32 I50 5 U 0 0 u 37 I50 5 t) 0 0 (l u 38 ISO 5 0 t) 0 n 0 4| ISO 4 0 t) 0 o u 42 I50 5 0 ti 0 u l) 43 I50 5 0 0 0 t t) 44 H0 5 0 t) t) 0 u 45 I 5 u 0 u (l t 49 I50 4 0 0 t) 0 u The compound for the I50 3 (l t) 0 u 0 compurison Untreated U 0 t) t) (1 plants rasr s Controlling test for inhibitting seed germination of weeds Soils containing a mixture of large crab-grass seeds and common purslane seeds was packed in a pot having a surface area of X 10 cm and immediately. an emulsifiable concentrate of a test compound prepared in similar manner to Example 13 was diluted with water to a specified concentration and the resulting diluted emulsion was sprayed on the surface area of the soil and thereby a controlling treatment was carried out. in the course of the 21st day after the treating step. a growth state of weeds was investigated. A judging standard for the growth state was the same as test I.

This investigating results are set forth in Table 6.

Table 6 Amount of eflective Growth state component large common g/ l 0:.) crab-grass purslane Test compound No.

The

compound for the comparison TEST 6 Test for foliar treatment Soils was packed in a pot and seeds of barnyard grass and smooth pigweed were sowed in the said soils and a covering soils were softly laid upon them and those seeds were made to grow in a greenhouse. In occasion that the seeds were germinated and. these seedlings were grown to a stage of sprouting the first leaf. an emulsifiable concentrate of a test compound prepared in similar manner to Example 13 was diluted with water to a specified concentration and the resulting diluted Table 7 Test Compound No.

Growth state barnyard smooth pigweed grass Amount of effective component (I! l m The com pound for the comparison lJh-l viauuuv-utt-uueauuu TEST 7 Test for soil treatment Soils were packed in a pot and about l5 grains of barnyard grass seeds were sowed on the said soils and a covering soils was laid on the seeds and those seeds were made to grow in a greenhouse. In the occasion that the seeds were germinated and its seedlings were grown to a stage of sprouting the first leaf. the said ot was maintained in a water stagnation conditions with 3 cm of depth and an emulsifiable concentrate of each test compound prepared in similar manner to Example 13 was diluted to an each specified concentration and the resulting each diluted emulsion was respectively poured into each spot. in the course of the 14th day and the 21st day after above treating step. the growth states of barnyard grass were respectively investigated.

The results are shown in Table 8 with the values ol 0-5 which have the same meaning of those of Test l.

Table 8 Test Amount of etTective Growth state compound component (g/IOa.) Mth day Zlst day 200 s s 60 I00 5 5 50 5 5 200 5 S 6! I00 5 i 50 4 5 200 5 t 63 I00 5 5 $0 5 Q 200 5 s 64 I00 5 i 50 S s 200 5 5 65 I00 5 5 $0 5 5 Compound 200 S 5 for the I00 4 4 comparison 50 2 2 TEST 8 Test for selective herbicidal effect Soils was packed in a vat having 780 cm of superficial area and seeds of barnyard grass, red bean. radish. cucumber. beet. soy bean and tomato were sowed on the said soil and a covering soils was softly laid upon them and then. those seeds were made to grow in a greenhouse. In the occasion that those seeds were germinated and the seedings of those crops were grown to a height of 5-8 cm. an emulsifiable concentrate of it test compound prepared in similar manner to Example 13 was diluted with water to a specified concentration and resulting diluted emulsion by l/lOa. of feed amount was respectively sprayed over stems and leaves of each crop. In the course of 10th day after above treating step. the growth states of those crops were investigated with judgement of naked eye. This investigating results in accordance with the judging standard of the growth state stigulated in test I are set forth in Table 9. 

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1 in which R1, R2 and R3 are ethyl group.
 3. A compound according to claim 1 in which R1 and R3 are ethyl group and R3 is allyl group.
 4. A compound according to claim 1 in which R1 is ethyl group, R2 is propyl group and R3 is ethyl group.
 5. A compound according to claim 1 in which R1 is ethyl group, R2 is propyl group and R3 is allyl group.
 6. A compound according to claim 1 in which R1 is propyl group, R2 and R3 are ethyl group.
 7. A compound according to claim 1 in which R1 is propyl group. R2 is ethyl group and R3 is allyl group
 8. A compound according to claim 1 in which R1 and R2 are propyl group and R3 is ethyl group.
 9. A compound according to claim 1 in which R1 and R2 are propyl group and R3 is allyl group. 